SAFETY DATA SHEET Based upon Regulation (EC) No. 1907/2006, as amended by Regulation (EC) No. 453/2010 manganese dioxide SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1 Product identifier: Product name : manganese dioxide Synonyms : slimes and sludges, zinc sulfate electrolytic; MnO2 rich material, cell mud, anode mud, MnO2 sludge, Pb Mn cell mud, manganese sludge, anode cleaning sludge Registration number REACH : 01-2119467168-30-0000 (Nyrstar Belgium NV/SA) 01-2119467168-30-0003 (Nyrstar Budel BV) 01-2119467168-30-0006 (Nyrstar France SAS) Product type REACH : Substance/UVCB : Transported isolated intermediate : On-site isolated intermediate CAS number : 69012-43-7 EC number : 273-742-8 1.2 Relevant identified uses of the substance or mixture and uses advised against:
1.2.1 Relevant identified uses Under Regulation (EC) No 1907/2006 the substance is defined as an on-site and transported isolated intermediate and must be used in correspondence to that status, including the application of strictly controlled conditions Industrial use: manufacturing of chemicals For further details concerning the management measures: see the attached annex
1.2.2 Uses advised against No uses advised against known 1.3 Details of the supplier of the safety data sheet:
Supplier of the safety data sheet
Manufacturer of the product
1.4 Emergency telephone number: 24h/24h (Telephone advice: English, French, German, Dutch): +32 14 58 45 45 (BIG) SECTION 2: Hazards identification 2.1 Classification of the substance or mixture:
Created by: Brandweerinformatiecentrum voor gevaarlijke stoffen vzw (BIG) Publication date: 2013-05-07 Technische Schoolstraat 43 A, B-2440 Geel Date of revision: 2013-12-10 http://www.big.be © BIG vzw Reason for revision: 1.2;8.1;8.2;15.1 134-16274-425-en Revision number: 0001 Product number: 28902 1 / 17 manganese dioxide
2.1.1 Classification according to Regulation EC No 1272/2008 Classified as dangerous according to the criteria of Regulation (EC) No 1272/2008 Class Category Hazard statements Carc. category 2 H351: Suspected of causing cancer. Repr. category 1A H360Df: May damage the unborn child. Suspected of damaging fertility. STOT RE category 1 H372: Causes damage to organs through prolonged or repeated exposure if swallowed and if inhaled. Acute Tox. category 4 H332: Harmful if inhaled. Acute Tox. category 4 H302: Harmful if swallowed. Aquatic Acute category 1 H400: Very toxic to aquatic life. Aquatic Chronic category 1 H410: Very toxic to aquatic life with long lasting effects.
2.1.2 Classification according to Directive 67/548/EEC-1999/45/EC Classified as dangerous in accordance with the criteria of Directives 67/548/EEC and 1999/45/EC Repr. Cat. 1; R61 - May cause harm to the unborn child. Repr. Cat. 3; R62 - Possible risk of impaired fertility. Carc. Cat. 3; R40 - Limited evidence of a carcinogenic effect Xn; R20/22 - 48/20/22 - Harmful by inhalation and if swallowed. Harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed. N; R50-53 - Very toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment. 2.2 Label elements:
Labelling according to Regulation EC No 1272/2008 (CLP)
Contains manganese dioxide; lead(II)sulfate. Signal word Danger H-statements H351 Suspected of causing cancer. H360Df May damage the unborn child. Suspected of damaging fertility. H372 Causes damage to organs through prolonged or repeated exposure if swallowed and if inhaled. H302 + H332 Harmful if swallowed or if inhaled. H410 Very toxic to aquatic life with long lasting effects. P-statements P202 Do not handle until all safety precautions have been read and understood. P281 Use personal protective equipment as required. P260 Do not breathe dust. P309 + P311 IF exposed or if you feel unwell: Call a POISON CENTER or doctor/physician. P304 + P340 IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing. P301 + P312 IF SWALLOWED: Call a POISON CENTER or doctor/physician if you feel unwell. 2.3 Other hazards:
CLP Slightly irritant to respiratory organs Slightly irritant to eyes SECTION 3: Composition/information on ingredients 3.1 Substances:
CAS No Classification Classification according to Name (REACH Registration No) Conc. (C) Note Remark EC No according to DSD/DPD CLP
1314-13-2 0% Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 2 / 17 manganese dioxide 1313-13-9 55.36% Xn; R20/22 Acute Tox. 4; H332 (1)(2) Component 215-202-6 SECTION 4: First aid measures 4.1 Description of first aid measures: General: Check the vital functions. Unconscious: maintain adequate airway and respiration. Respiratory arrest: artificial respiration or oxygen. Cardiac arrest: perform resuscitation. Victim conscious with laboured breathing: half-seated. Victim in shock: on his back with legs slightly raised. Vomiting: prevent asphyxia/aspiration pneumonia. Prevent cooling by covering the victim (no warming up). Keep watching the victim. Give psychological aid. Keep the victim calm, avoid physical strain. Depending on the victim's condition: doctor/hospital. After inhalation: Remove the victim into fresh air. Respiratory problems: consult a doctor/medical service. After skin contact: Rinse with water. Soap may be used. Take victim to a doctor if irritation persists. After eye contact: Rinse with water. Do not apply neutralizing agents. Take victim to an ophthalmologist if irritation persists. After ingestion: Rinse mouth with water. Immediately after ingestion: give lots of water to drink. Do not induce vomiting. Consult a doctor/medical service if you feel unwell. 4.2 Most important symptoms and effects, both acute and delayed: 4.2.1 Acute symptoms After inhalation: No effects known. After skin contact: No effects known. After eye contact: No effects known. After ingestion: Vomiting. Abdominal pain. Diarrhoea. Irritation of the gastric/intestinal mucosa. 4.2.2 Delayed symptoms No effects known. 4.3 Indication of any immediate medical attention and special treatment needed: If applicable and available it will be listed below. SECTION 5: Firefighting measures The information in this section is a general description. If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. 5.1 Extinguishing media: 5.1.1 Suitable extinguishing media: Adapt extinguishing media to the environment. 5.1.2 Unsuitable extinguishing media: No unsuitable extinguishing media known. 5.2 Special hazards arising from the substance or mixture: On burning: release of harmful/irritant gases/vapours. 5.3 Advice for firefighters: 5.3.1 Instructions: Take account of environmentally hazardous firefighting water. Use water moderately and if possible collect or contain it. 5.3.2 Special protective equipment for fire-fighters: Gloves. Safety glasses. Protective clothing. Reactivity hazard: compressed air/oxygen apparatus. Reactivity hazard: gas-tight suit. Large spills/in enclosed spaces: compressed air apparatus. Heat/fire exposure: compressed air/oxygen apparatus. Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 3 / 17 manganese dioxide SECTION 6: Accidental release measures The information in this section is a general description. If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. 6.1 Personal precautions, protective equipment and emergency procedures: Prevent dust cloud formation. No naked flames. 6.1.1 Protective equipment for non-emergency personnel See heading 8.2 6.1.2 Protective equipment for emergency responders Gloves. Safety glasses. Protective clothing. Reactivity hazard: compressed air/oxygen apparatus. Reactivity hazard: gas-tight suit. Large spills/in enclosed spaces: compressed air apparatus. Suitable protective clothing See heading 8.2 6.2 Environmental precautions: Contain released substance, pump into suitable containers. Plug the leak, cut off the supply. Dam up the solid spill. Take account of toxic/corrosive precipitation water. Prevent soil and water pollution. Prevent spreading in sewers. 6.3 Methods and material for containment and cleaning up: Prevent dust cloud formation. Scoop solid spill into closing containers. Carefully collect the spill/leftovers. Clean contaminated surfaces with an excess of water. Wash clothing and equipment after handling. Take collected spill to manufacturer/competent authority. 6.4 Reference to other sections: See heading 13. SECTION 7: Handling and storage The information in this section is a general description. If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. 7.1 Precautions for safe handling: Avoid raising dust. Keep away from naked flames/heat. Observe very strict hygiene - avoid contact. Keep container tightly closed. Remove contaminated clothing immediately. Do not discharge the waste into the drain. 7.2 Conditions for safe storage, including any incompatibilities: 7.2.1 Safe storage requirements: Store in a dry area. Keep only in the original container. Store at ambient temperature. Meet the legal requirements. 7.2.2 Keep away from: Heat sources, combustible materials, oxidizing agents, reducing agents, (strong) acids, organic materials. 7.2.3 Suitable packaging material: No data available 7.2.4 Non suitable packaging material: No data available 7.3 Specific end use(s): If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. SECTION 8: Exposure controls/personal protection 8.1 Control parameters: 8.1.1 Occupational exposure a) Occupational exposure limit values If limit values are applicable and available these will be listed below. The Netherlands Calciumsulfaat Time-weighted average exposure limit 8 h 0.5 mg/m³ Private occupational exposure limit value Lood en anorg. verbindingen (rook en Time-weighted average exposure limit 8 h 0.15 mg/m³ (a.31) Private occupational exposure limit stof) (als Pb) value; a.31: as Pb; fume/dust Mangaanverbindingen (als Mn) Short time value 3 mg/m³ (a.27) Private occupational exposure limit value; a.27: as Mn Time-weighted average exposure limit 8 h 1 mg/m³ (a.27) Private occupational exposure limit value; a.27: as Mn Zinkoxide (rook) Time-weighted average exposure limit 8 h 5 mg/m³ (a.53) Private occupational exposure limit value; a.53: fume EU Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 4 / 17 manganese dioxide Inorganic lead and its compounds Time-weighted average exposure limit 8 h 0,15 mg/m³ Binding occupational exposure limit value Belgium Calcium (sulfate de) (anhydrate, Time-weighted average exposure limit 8 h 10 mg/m³ hemihydrate, dihydrate, gypse) Manganèse et ses composés (en Mn) Time-weighted average exposure limit 8 h 0.2 mg/m³ Plomb inorg. (poussières et fumées) (en Time-weighted average exposure limit 8 h 0.15 mg/m³ Pb) Zinc (oxyde de) ( fumées) Short time value 10 mg/m³ Time-weighted average exposure limit 8 h 5 mg/m³ USA (TLV-ACGIH) Lead, inorganic compounds, as Pb Time-weighted average exposure limit 8 h 0.05 mg/m³ TLV - Adopted Value Zinc oxide Short time value 10 mg/m³ (R) TLV - Adopted Value; (R): Respirable fraction Time-weighted average exposure limit 8 h 2 mg/m³ (R) TLV - Adopted Value; (R): Respirable fraction Calcium sulfate Time-weighted average exposure limit 8 h 10 mg/m³ (E) TLV - Adopted Value; (E): The value is for particulate matter containing no asbestos and < 1% crystalline silica Manganese, inorganic compounds, as Time-weighted average exposure limit 8 h 0.1 mg/m³ (I) TLV - Adopted Value; (I): Inhalable Mn fraction Germany Calciumsulfat Time-weighted average exposure limit 8 h 6 mg/m³ TRGS 900 anorganischen Manganverbindungen Time-weighted average exposure limit 8 h 0.5 mg/m³ TRGS 900 Blei und anorganischen Time-weighted average exposure limit 8 h 0.1 mg/m³ TRGS 505 Bleiverbindungen France Calcium (sulfate de) Time-weighted average exposure limit 8 h 10 mg/m³ VL: Valeur non réglementaire indicative Zinc (oxyde de, fumées) Time-weighted average exposure limit 8 h 5 mg/m³ VL: Valeur non réglementaire indicative Zinc (oxyde de, poussières) Time-weighted average exposure limit 8 h 10 mg/m³ VL: Valeur non réglementaire indicative Plomb métallique et composés, en Pb Time-weighted average exposure limit 8 h 0.1 mg/m³ VRC: Valeur réglementaire contraignante UK Manganese inorganic compounds (as Time-weighted average exposure limit 8 h 0.5 mg/m³ Workplace exposure limit (EH40/2005) Mn) Gypsum inhalable dust Time-weighted average exposure limit 8 h 10 mg/m³ Workplace exposure limit (EH40/2005) Gypsum respirable dust Time-weighted average exposure limit 8 h 4 mg/m³ Workplace exposure limit (EH40/2005) Lead other than lead alkyls Time-weighted average exposure limit 8 h 0,15 mg/cm³ Occupational exposure limit (Control of lead at work) b) National biological limit values If limit values are applicable and available these will be listed below. 8.1.2 Sampling methods Product name Test Number Lead OSHA ID 121 Lead OSHA ID 125G Lead, Inorganic surface dusts (as Pb) OSHA ID 121 Manganese OSHA ID 121 Manganese OSHA ID 125 Manganese OSHA ID 125G Sulfites, & Sulfates NIOSH 6004 Zinc (Elements) NIOSH 7300 Zinc Oxide NIOSH 7502 Zinc Oxide OSHA ID 121 Zinc Oxide NIOSH 7030 Zinc Oxide Fume OSHA ID 125 8.1.3 Applicable limit values when using the substance or mixture as intended If limit values are applicable and available these will be listed below. 8.1.4 DNEL/PNEC values DNEL - Workers Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 5 / 17 manganese dioxide zinc oxide Effect level (DNEL/DMEL) Type Value Remark DNEL Long-term systemic effects dermal 83 mg/kg bw/day Long-term systemic effects inhalation 5 mg/m³ manganese dioxide Effect level (DNEL/DMEL) Type Value Remark DNEL Long-term systemic effects inhalation 0.2 mg/m³ Long-term systemic effects dermal 0.00414 mg/kg bw/day calcium sulfate Effect level (DNEL/DMEL) Type Value Remark DNEL Acute systemic effects inhalation 5082 mg/m³ Long-term systemic effects inhalation 21.17 mg/m³ DNEL - General population zinc oxide Effect level (DNEL/DMEL) Type Value Remark DNEL Long-term systemic effects dermal 83 mg/kg bw/day Long-term systemic effects inhalation 2.5 mg/m³ Long-term systemic effects oral 0.83 mg/kg bw/day manganese dioxide Effect level (DNEL/DMEL) Type Value Remark DNEL Long-term systemic effects inhalation 0.043 mg/m³ Long-term systemic effects dermal 0.0021 mg/kg bw/day calcium sulfate Effect level (DNEL/DMEL) Type Value Remark DNEL Acute systemic effects inhalation 3811 mg/m³ Acute -systemic effects oral 11.4 mg/kg bw/day Long-term systemic effects inhalation 5.29 mg/m³ Long-term systemic effects oral 1.52 mg/kg bw/day PNEC zinc oxide Compartments Value Remark Fresh water 20.6 µg/l Marine water 6.1 µg/l STP 52 µg/l Fresh water sediment 117.8 mg/kg sediment dw Marine water sediment 56.5 mg/kg sediment dw Soil 35.6 mg/kg soil dw 8.1.5 Control banding If applicable and available it will be listed below. 8.2 Exposure controls: The information in this section is a general description. If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. 8.2.1 Appropriate engineering controls Avoid raising dust. Keep away from naked flames/heat. Measure the concentration in the air regularly. Carry operations in the open/under local exhaust/ventilation or with respiratory protection. 8.2.2 Individual protection measures, such as personal protective equipment Observe very strict hygiene - avoid contact. Keep container tightly closed. Do not eat, drink or smoke during work. a) Respiratory protection: Dust production: dust mask with filter type P3. High dust production: self-contained breathing apparatus. b) Hand protection: Gloves. - materials (good resistance) Butyl rubber, chlorinated polyethylene, nitrile rubber, neoprene, PVC, chlorinated polyethylene. c) Eye protection: Safety glasses. In case of dust production: protective goggles. d) Skin protection: Protective clothing. Dustproof clothing. 8.2.3 Environmental exposure controls: See headings 6.2, 6.3 and 13 SECTION 9: Physical and chemical properties Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 6 / 17 manganese dioxide 9.1 Information on basic physical and chemical properties: Physical form Solid Odour Odourless Odour threshold Not applicable Colour Grey to brown-black Particle size D50 = 929 mm D80 = 2083 mm Explosion limits No data available Flammability Non combustible Log Kow Not applicable Dynamic viscosity No data available Kinematic viscosity No data available Melting point 193 °C ; 1013 hPa Boiling point No data available Flash point Not applicable Evaporation rate No data available Vapour pressure No data available Relative vapour density Not applicable Solubility water ; insoluble Relative density 4.09 ; 20 °C Decomposition temperature No data available Auto-ignition temperature No data available Explosive properties No chemical group associated with explosive properties Oxidising properties No chemical group associated with oxidising properties pH No data available Physical hazards No physical hazard class 9.2 Other information: No data available SECTION 10: Stability and reactivity 10.1 Reactivity: No data available. 10.2 Chemical stability: Stable under normal conditions. 10.3 Possibility of hazardous reactions: Reacts with many compounds: (increased) risk of fire/explosion. Reacts with (some) acids: release of toxic and corrosive gases/vapours. 10.4 Conditions to avoid: Avoid raising dust. Keep away from naked flames/heat. 10.5 Incompatible materials: Combustible materials, oxidizing agents, reducing agents, (strong) acids, organic materials. 10.6 Hazardous decomposition products: No data available. SECTION 11: Toxicological information 11.1 Information on toxicological effects: 11.1.1 Test results Acute toxicity manganese dioxide No (test)data available Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 7 / 17 manganese dioxide zinc oxide Route of exposure Parameter Method Value Exposure time Species Gender Value determination Oral LD50 Equivalent to OECD > 5000 mg/kg Rat Experimental value 401 Dermal LD50 > 7940 mg/kg Rabbit Literature study Inhalation (dust) LC50 Equivalent to OECD >5.7 mg/l 4 h Rat Experimental value 403 lead(II)sulfate Route of exposure Parameter Method Value Exposure time Species Gender Value determination Oral category 4 Annex VI Inhalation category 4 Annex VI manganese dioxide Route of exposure Parameter Method Value Exposure time Species Gender Value determination Oral category 2 Literature study Inhalation category 2 Literature study calcium sulfate Route of exposure Parameter Method Value Exposure time Species Gender Value determination Oral LD50 OECD 420 >1584 mg/kg bw Rat Female Experimental value Inhalation (dust) LC50 OECD 403 >2.61 mg/l air 4 h Rat Male/female Experimental value Conclusion Harmful if swallowed. Harmful if inhaled. Low acute toxicity by the dermal route Corrosion/irritation manganese dioxide No (test)data available zinc oxide Route of exposure Result Method Exposure time Time point Species Value determination Eye Not irritating OECD 405 24 h 24; 72 hours Rabbit Experimental value Skin Not irritating OECD 404 24 h 24 hours Rabbit Experimental value calcium sulfate Route of exposure Result Method Exposure time Time point Species Value determination Eye Not irritating OECD 405 72 hours Rabbit Experimental value Skin Not irritating OECD 404 4 h 72 hours Rabbit Experimental value Conclusion Not classified as irritating to the skin Not classified as irritating to the eyes Respiratory or skin sensitisation manganese dioxide No (test)data available zinc oxide Route of exposure Result Method Exposure time Observation time Species Gender Value point determination Skin Not sensitizing Human observation 2 days 72 hours Human Experimental value (continuous) calcium sulfate Route of exposure Result Method Exposure time Observation time Species Gender Value point determination Skin Not sensitizing OECD 406 6 h 24; 48 hours Guinea pig Male Experimental value Conclusion Not classified as sensitizing for skin Specific target organ toxicity manganese dioxide No (test)data available Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 8 / 17 manganese dioxide zinc oxide Route of exposure Parameter Method Value Organ Effect Exposure time Species Gender Value determination Oral NOEL OECD 408 3000 ppm No effect 13 weeks (daily) Rat Male/femal Read-across e Inhalation NOAEL 2.7 mg/m³ air No effect 5 days (3h/day) Guinea pig Male Experimental (aerosol) value lead(II)sulfate Route of exposure Parameter Method Value Organ Effect Exposure time Species Gender Value determination Oral STOT RE cat.2 Annex VI Dermal STOT RE cat.2 Annex VI Inhalation STOT RE cat.2 Annex VI calcium sulfate Route of exposure Parameter Method Value Organ Effect Exposure time Species Gender Value determination Oral NOAEL OECD 422 79 mg/kg Blood No effect 35 day(s) Rat Male Experimental bw/day value Oral LOAEL OECD 422 237 mg/kg Blood Change in the 35 day(s) Rat Male Experimental bw/day haemogramme value /blood composition Conclusion Causes damage to organs through prolonged or repeated exposure if swallowed. Causes damage to organs through prolonged or repeated exposure if inhaled. Mutagenicity (in vitro) manganese dioxide No (test)data available zinc oxide Result Method Test substrate Effect Value determination Negative Equivalent to OECD 471 Bacteria (S.typhimurium) No effect Experimental value lead(II)sulfate Result Method Test substrate Effect Value determination Negative Ames test Experimental value Ambiguous Experimental value calcium sulfate Result Method Test substrate Effect Value determination Negative with metabolic OECD 471 Bacteria (S.typhimurium) No effect Experimental value activation, negative without metabolic activation Negative with metabolic OECD 471 Escherichia coli No effect Experimental value activation, negative without metabolic activation Negative with metabolic OECD 476 Mouse (lymphoma L5178Y No effect Experimental value activation, negative without cells) metabolic activation Mutagenicity (in vivo) manganese dioxide No (test)data available zinc oxide Result Method Exposure time Test substrate Gender Organ Value determination Negative OECD 474 Mouse Male Experimental value calcium sulfate Result Method Exposure time Test substrate Gender Organ Value determination Negative OECD 474 Mouse Male Blood Experimental value Carcinogenicity manganese dioxide No (test)data available Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 9 / 17 manganese dioxide calcium sulfate Route of Parameter Method Value Exposure time Species Gender Value Organ Effect exposure determination Oral NOAEL Other 256 mg/kg 104 weeks (daily) Rat Male Experimental No effect bw/day value Oral NOAEL Other 284 mg/kg 104 weeks (daily) Rat Female Experimental No effect bw/day value Reproductive toxicity manganese dioxide No (test)data available zinc oxide Parameter Method Value Exposure Species Gender Effect Organ Value time determination Developmental toxicity NOAEL 88 mg/kg 5 days Guinea pig No effect Read-across bw/day (gestation, daily) Effects on fertility NOAEL (F1) Equivalent to 7.5 mg/kg 22 weeks Rat Male/female No effect Read-across OECD 416 bw/day (daily) lead(II)sulfate Parameter Method Value Exposure Species Gender Effect Organ Value time determination Developmental toxicity category 1A Annex VI Effects on fertility category 2 Annex VI calcium sulfate Parameter Method Value Exposure Species Gender Effect Organ Value time determination Developmental toxicity NOAEL Equivalent to 1600 mg/kg 10 day(s) Mouse No effect General Experimental OECD 414 bw/day value NOAEL Equivalent to 1600 mg/kg 10 day(s) Rat No effect General Experimental OECD 414 bw/day value NOAEL Equivalent to 1600 mg/kg 13 day(s) Rabbit No effect General Experimental OECD 414 bw/day value Effects on fertility NOAEL OECD 422 790 mg/kg 2 week(s) Rat Male/female No effect Experimental bw/day value Conclusion CMR Suspected of causing cancer. May damage the unborn child. Suspected of damaging fertility. Toxicity other effects manganese dioxide No (test)data available Chronic effects from short and long-term exposure manganese dioxide ON CONTINUOUS/REPEATED EXPOSURE/CONTACT: Feeling of weakness. Loss of appetite. Loss of weight. Sleeplessness. Brain affection. Behavioural disturbances. Delusions. Disturbed tactile sensibility. Movement disturbances. Coordination disorders. Disturbed motor response. Tremor. Coughing. Respiratory difficulties. Risk of pneumonia. Change in the haemogramme/blood composition. Impairment of the blood forming system. Possible premature birth. Discolouration of the gums. SECTION 12: Ecological information 12.1 Toxicity: manganese dioxide Parameter Method Value Duration Species Test design Fresh/salt Value determination water Acute toxicity invertebrates LC50 US EPA 73.56 µg/l 48 h Ceriodaphnia Semi-static Fresh water Read-across dubia Long-term toxicity fish EC10 17.8 µg/l 7 day(s) Cyprinus carpio Flow-through Fresh water Read-across system Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 10 / 17 manganese dioxide zinc oxide Parameter Method Value Duration Species Test design Fresh/salt Value determination water Acute toxicity fishes LC50 ASTM E729- 0.169 mg/l 96 h Oncorhynchus Static system Fresh water Read-across; Zinc ion 88 mykiss Acute toxicity invertebrates LC50 OECD 202 0.33 - 0.66 48 h Daphnia magna Static system Fresh water Read-across; Zinc ion mg/l Toxicity algae and other aquatic IC50 OECD 201 0.136 mg/l 72 h Pseudokirchnerie Static system Fresh water Experimental value; plants lla subcapitata Zinc ion Long-term toxicity fish NOEC OECD 215 0.199 mg/l 30 day(s) Oncorhynchus Flow-through Fresh water Read-across; Zinc ion mykiss system Long-term toxicity aquatic NOEC 0.31 mg/l 21 day(s) Daphnia magna Semi-static Fresh water Read-across; Zinc ion invertebrates Toxicity aquatic micro- EC50 Equivalent to 5.2 mg/l 3 h Activated sludge Static system Fresh water Read-across; organisms OECD 209 Inhibitory lead(II)sulfate Parameter Method Value Duration Species Test design Fresh/salt Value determination water Acute toxicity fishes TLm 7.48 mg/l 96 h Pimephales Literature study; promelas Lead ion Acute toxicity invertebrates LC50 0.3 mg/l 48 h Daphnia magna Literature study; Lead ion Toxicity algae and other aquatic EC50 0.14 mg/l Selenastrum Literature study; plants capricornutum Lead ion calcium sulfate Parameter Method Value Duration Species Test design Fresh/salt Value determination water Acute toxicity fishes LC50 2980 mg/l 96 h Lepomis macrochirus Conclusion Very toxic to aquatic life with long lasting effects. 12.2 Persistence and degradability: Biodegradability: not applicable 12.3 Bioaccumulative potential: manganese dioxide Log Kow Method Remark Value Temperature Value determination Not applicable zinc oxide Log Kow Method Remark Value Temperature Value determination 1.53 Estimated value lead(II)sulfate Log Kow Method Remark Value Temperature Value determination 1.13 Estimated value manganese dioxide Log Kow Method Remark Value Temperature Value determination No data available calcium sulfate Log Kow Method Remark Value Temperature Value determination No data available strontium sulphate Log Kow Method Remark Value Temperature Value determination No data available Conclusion No straightforward conclusion can be drawn based upon the available numerical values Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 11 / 17 manganese dioxide 12.4 Mobility in soil: zinc oxide (log) Koc Parameter Method Value Value determination log Koc 2.2 Literature study Conclusion No straightforward conclusion can be drawn based upon the available numerical values 12.5 Results of PBT and vPvB assessment: The criteria of PBT and vPvB as listed in Annex XIII of Regulation (EC) No 1907/2006 do not apply to inorganic substances. 12.6 Other adverse effects: manganese dioxide Global warming potential (GWP) None of the known components is included in the list of substances which may contribute to the greenhouse effect (Regulation (EC) No 842/2006) Ozone-depleting potential (ODP) Not classified as dangerous for the ozone layer (Regulation (EC) No 1005/2009) zinc oxide Ground water Ground water pollutant SECTION 13: Disposal considerations The information in this section is a general description. If available, the documentation for on-site isolated intermediates will be attached in annex to support safe handling arrangements. 13.1 Waste treatment methods: 13.1.1 Provisions relating to waste Waste material code (Directive 2008/98/EC, Decision 2000/0532/EC). 06 03 13* (solid salts and solutions containing heavy metals). Depending on branch of industry and production process, also other waste codes may be applicable. Hazardous waste according to Directive 2008/98/EC. 13.1.2 Disposal methods Recycle/reuse. Remove waste in accordance with local and/or national regulations. Hazardous waste shall not be mixed together with other waste. Different types of hazardous waste shall not be mixed together if this may entail a risk of pollution or create problems for the further management of the waste. Hazardous waste shall be managed responsibly. All entities that store, transport or handle hazardous waste shall take the necessary measures to prevent risks of pollution or damage to people or animals. Do not discharge into surface water (Directive 2000/60/EC, Council decision 2455/2001/EC). Treat using the best available techniques before discharge into drains or the aquatic environment. 13.1.3 Packaging/Container Waste material code packaging (Directive 2008/98/EC). 15 01 10* (packaging containing residues of or contaminated by dangerous substances). SECTION 14: Transport information Road (ADR) 14.1 UN number: UN number 3077 14.2 UN proper shipping name: Proper shipping name Environmentally hazardous substance, solid, n.o.s. Techn./chem. name ADR lead(II)sulfate 14.3 Transport hazard class(es): Hazard identification number 90 Class 9 Classification code M7 14.4 Packing group: Packing group III Labels 9 14.5 Environmental hazards: Environmentally hazardous substance mark yes 14.6 Special precautions for user: Special provisions 274 Special provisions 335 Special provisions 601 Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 12 / 17 manganese dioxide Limited quantities Combination packagings: not more than 5 kg per inner packaging for solids. A package shall not weigh more than 30 kg. (gross mass) Rail (RID) 14.1 UN number: UN number 3077 14.2 UN proper shipping name: Proper shipping name Environmentally hazardous substance, solid, n.o.s. Techn./chem. name RID lead(II)sulfate 14.3 Transport hazard class(es): Hazard identification number 90 Class 9 Classification code M7 14.4 Packing group: Packing group III Labels 9 14.5 Environmental hazards: Environmentally hazardous substance mark yes 14.6 Special precautions for user: Special provisions 274 Special provisions 335 Special provisions 601 Limited quantities Combination packagings: not more than 5 kg per inner packaging for solids. A package shall not weigh more than 30 kg. (gross mass) Inland waterways (ADN) 14.1 UN number: UN number 3077 14.2 UN proper shipping name: Proper shipping name Environmentally hazardous substance, solid, n.o.s. Techn./chem. name ADN lead(II)sulfate 14.3 Transport hazard class(es): Class 9 Classification code M7 14.4 Packing group: Packing group III Labels 9 14.5 Environmental hazards: Environmentally hazardous substance mark yes 14.6 Special precautions for user: Special provisions 274 Special provisions 335 Special provisions 601 Limited quantities Combination packagings: not more than 5 kg per inner packaging for solids. A package shall not weigh more than 30 kg. (gross mass) Sea (IMDG/IMSBC) 14.1 UN number: UN number 3077 14.2 UN proper shipping name: Proper shipping name Environmentally hazardous substance, solid, n.o.s. Techn./chem. name IMO lead(II)sulfate 14.3 Transport hazard class(es): Class 9 14.4 Packing group: Packing group III Labels 9 14.5 Environmental hazards: Marine pollutant P Environmentally hazardous substance mark yes 14.6 Special precautions for user: Special provisions 274 Special provisions 335 Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 13 / 17 manganese dioxide Special provisions 966 Special provisions 967 Limited quantities Combination packagings: not more than 5 kg per inner packaging for solids. A package shall not weigh more than 30 kg. (gross mass) 14.7 Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code: Annex II of MARPOL 73/78 Not applicable Air (ICAO-TI/IATA-DGR) 14.1 UN number: UN number 3077 14.2 UN proper shipping name: Proper shipping name Environmentally hazardous substance, solid, n.o.s. Techn./chem. name ICAO lead(II)sulfate 14.3 Transport hazard class(es): Class 9 14.4 Packing group: Packing group III Labels 9 14.5 Environmental hazards: Environmentally hazardous substance mark yes 14.6 Special precautions for user: Special provisions A97 Special provisions A158 Special provisions A179 Passenger and cargo transport: limited quantities: maximum net quantity 30 kg G per packaging SECTION 15: Regulatory information European legislation: REACH registration This substance is handled under Strictly Controlled Conditions in accordance with Reach regulation Article 17(3) for on-site isolated intermediates and, in case the substance is transported to other sites for further processing, the substance should be handled at these sites under Strictly Controlled Conditions as specified in Reach regulation Article 18(4). Site documentation to support safe handling arrangements including the selection of engineering, administrative and personal protective equipment controls in accordance with risk based management systems is available at each manufacturing site. Written confirmation of application of Strictly Controlled Conditions should be available at the premises of every affected Distributor and Downstream Processor/User of the Registrants’ intermediate. Information exposure scenarios This safety data sheet does not contain an exposure scenario; exempted as (isolated) intermediate REACH Annex XVII - Restriction Contains component(s) subject to restrictions of Annex XVII of Regulation (EC) No 1907/2006: restrictions on the manufacture, placing on the market and use of certain dangerous substances, mixtures and articles. Designation of the substance, of the group of Conditions of restriction substances or of the mixture · lead(II)sulfate Lead sulphates; PbSO 4 Shall not be placed on the market, or used, as substances or in mixtures, where the substance or mixture is intended for use as paint. However, Member States may, in accordance with the provisions of International Labour Organization (ILO) Convention 13, permit the use on their territory of the substance or mixture for the restoration and maintenance of works of art and historic buildings and their interiors, as well as the placing on the market for such use. Where a Member State makes use of this derogation, it shall inform the Commission thereof. · lead(II)sulfate Substances which appear in Part 3 of Annex VI Without prejudice to the other parts of this Annex the following shall apply to entries 28 to to Regulation (EC) No 1272/2008 classified as 30:1. Shall not be placed on the market, or used, toxic to reproduction category 1A or 1B (Table — as substances, 3.1) or toxic to reproduction category 1 or 2 — as constituents of other substances, or, (Table 3.2) and listed as follows: - — in mixtures, for supply to the general public when the individual concentration in the Reproductive toxicant category 1A adverse substance or mixture is equal to or greater than: effects on sexual function and fertility or on — either the relevant specific concentration limit specified in Part 3 of Annex VI to development (Table 3.1) or reproductive Regulation (EC) No 1272/2008, or, toxicant category 1 with R60 (May impair — the relevant concentration specified in Directive 1999/45/EC where no specific fertility) or R61 (May cause harm to the concentration limit is set out in Part 3 of Annex VI to Regulation (EC) No 1272/2008. Without unborn child) (Table 3.2) listed in Appendix 5 - prejudice to the implementation of other Community provisions relating to the classification, Reproductive toxicant category 1B adverse packaging and labelling of substances and mixtures, suppliers shall ensure before the placing effects on sexual function and fertility or on on the market that the packaging of such substances and mixtures is marked visibly, legibly development (Table 3.1) or reproductive and indelibly as follows: “Restricted to professional users”.2. By way of derogation, toxicant category 2 with R60 (May impair paragraph 1 shall not apply to: fertility) or R61 (May cause harm to the (a) medicinal or veterinary products as defined by Directive 2001/82/EC and Directive unborn child) (Table 3.2) listed in Appendix 6 2001/83/EC; (b) cosmetic products as defined by Directive 76/768/EEC; Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 14 / 17 manganese dioxide (c) the following fuels and oil products: — motor fuels which are covered by Directive 98/70/EC, — mineral oil products intended for use as fuel in mobile or fixed combustion plants, — fuels sold in closed systems (e.g. liquid gas bottles); (d) artists’ paints covered by Directive 1999/45/EC; (e) the substances listed in Appendix 11, column 1, for the applications or uses listed in Appendix 11, column 2. Where a date is specified in column 2 of Appendix 11, the derogation shall apply until the said date. · lead(II)sulfate Lead and its compounds 1. Shall not be placed on the market or used in any individual part of jewellery articles if the concentration of lead (expressed as metal) in such a part is equal to or greater than 0,05 % by weight.2. For the purposes of paragraph 1: (i) "jewellery articles" shall include jewellery and imitation jewellery articles and hair accessories, including: (a) bracelets, necklaces and rings; (b) piercing jewellery; (c) wrist watches and wrist-wear; (d) brooches and cufflinks; (ii) "any individual part" shall include the materials from which the jewellery is made, as well as the individual components of the jewellery articles.3. Paragraph 1 shall also apply to individual parts when placed on the market or used for jewellery-making.4. By way of derogation, paragraph 1 shall not apply to: (a) crystal glass as defined in Annex I (categories 1, 2, 3 and 4) to Council Directive 69/493/EEC (*); (b) internal components of watch timepieces inaccessible to consumers; (c) non-synthetic or reconstructed precious and semiprecious stones (CN code 7103, as established by Regulation (EEC) No 2658/87), unless they have been treated with lead or its compounds or mixtures containing these substances; (d) enamels, defined as vitrifiable mixtures resulting from the fusion, vitrification or sintering of minerals melted at a temperature of at least 500 °C. (*) OJ L 326, 29.12.1969, p. 36.5. By way of derogation, paragraph 1 shall not apply to jewellery articles placed on the market for the first time before 9 October 2013 and jewellery articles produced before 10 December 1961.6. By 9 October 2017, the Commission shall re-evaluate this entry in the light of new scientific information, including the availability of alternatives and the migration of lead from the articles referred to in paragraph 1 and, if appropriate, modify this entry accordingly. National legislation The Netherlands manganese dioxide Waste identification (the LWCA (the Netherlands): KGA category 05 Netherlands) Waterbezwaarlijkheid 1 lead(II)sulfate SZW - List of reprotoxic Possible risk of impaired fertility substances (fertility) SZW - List of reprotoxic Hazardous to the foetus substances (development) manganese dioxide SZW - List of reprotoxic Possible risk of impaired fertility substances (fertility) SZW - List of reprotoxic Possibly hazardous to the foetus substances (development) National legislation Germany manganese dioxide WGK 3; Classification water polluting based on the components in compliance with Verwaltungsvorschrift wassergefährdender Stoffe (VwVwS) of 27 July 2005 (Anhang 4) zinc oxide TA-Luft TA-Luft Klasse 5.2.5/I Schwangerschaft Gruppe C Schwangerschaft Gruppe C MAK 8-Stunden-Mittelwert Zink und seine anorganischen Verbindungen (alveolengängige Fraktion); 0,1 mg/m³; gemessen als alveolengängige mg/m³ Fraktion (vgl. Abschn. Vd) S. 191) Zink und seine anorganischen Verbindungen (einatembare Fraktion); 2 mg/m³; gemessen als einatembare Fraktion (vgl. Abschn. Vd) S. 191) lead(II)sulfate MAK - Krebserzeugend 2 Kategorie MAK - Keimzellmutagen 3A Kategorie TA-Luft TA-Luft Klasse 5.2.2/II manganese dioxide TA-Luft TA-Luft Klasse 5.2.2/III Schwangerschaft Gruppe C MAK 8-Stunden-Mittelwert Mangan und seine anorganischen Verbindungen (einatembare Fraktion); 0,2 mg/m³; gemessen als einatembare Fraktion mg/m³ (vgl. Abschn. Vd) S. 191) Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 15 / 17 manganese dioxide calcium sulfate TA-Luft TA-Luft Klasse 5.2.1 Schwangerschaft Gruppe C Schwangerschaft Gruppe C Schwangerschaft Gruppe C Schwangerschaft Gruppe C MAK 8-Stunden-Mittelwert Calciumsulfat (alveolengängige Fraktion); 1.5 mg/m³; gemessen als alveolengängige Fraktion (vgl. Abschn. Vd) S. 191) mg/m³ Calciumsulfat (einatembare Fraktion); 4 mg/m³; gemessen als einatembare Fraktion (vgl. Abschn. Vd) S. 191) Calciumsulfat (alveolengängige Fraktion); 1.5 mg/m³; gemessen als alveolengängige Fraktion (vgl. Abschn. Vd) S. 191) Calciumsulfat (einatembare Fraktion); 4 mg/m³; gemessen als einatembare Fraktion (vgl. Abschn. Vd) S. 191) National legislation France manganese dioxide No data available lead(II)sulfate Catégorie cancérogène (C1A,C1B,C2) National legislation Belgium manganese dioxide No data available Other relevant data manganese dioxide No data available lead(II)sulfate TLV - Carcinogen Lead, inorganic compounds, as Pb; A3 manganese dioxide TLV - Carcinogen Manganese, inorganic compounds, as Mn; A4 15.2 Chemical safety assessment: No chemical safety assessment is required; registered as an isolated intermediate. SECTION 16: Other information Information based on classification according to CLP Labelling according to Directive 67/548/EEC-1999/45/EC (DSD/DPD) Not listed in Annex I of Directive 67/548/EEC et sequens. Labelling established on the basis of the available data. Labels Toxic Dangerous for the environment Contains: manganese dioxide; lead(II)sulfate. R-phrases 61 May cause harm to the unborn child 20/22 Also harmful by inhalation and if swallowed 40 Limited evidence of a carcinogenic effect 48/20/22 Also harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed 50/53 Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment 62 Possible risk of impaired fertility S-phrases 53 Avoid exposure - obtain special instructions before use 20 When using do not eat or drink 36 Wear suitable protective clothing 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible) 57 Use appropriate container to avoid environmental contamination Full text of any R-phrases referred to under headings 2 and 3: R20/22 Harmful by inhalation and if swallowed R33 Danger of cumulative effects R40 Limited evidence of a carcinogenic effect Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 16 / 17 manganese dioxide R48/20/22 Harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed R50 Very toxic to aquatic organisms R53 May cause long-term adverse effects in the aquatic environment R61 May cause harm to the unborn child R62 Possible risk of impaired fertility Full text of any H-statements referred to under headings 2 and 3: H302 Harmful if swallowed. H332 Harmful if inhaled. H351 Suspected of causing cancer. H360Df May damage the unborn child. Suspected of damaging fertility. H372 Causes damage to organs through prolonged or repeated exposure if swallowed and if inhaled. H373 May cause damage to organs through prolonged or repeated exposure. H400 Very toxic to aquatic life. H410 Very toxic to aquatic life with long lasting effects. (*) = INTERNAL CLASSIFICATION BY BIG PBT-substances = persistent, bioaccumulative and toxic substances DSD Dangerous Substance Directive DPD Dangerous Preparation Directive CLP (EU-GHS) Classification, labelling and packaging (Globally Harmonised System in Europe) Specific concentration limits CLP lead(II)sulfate C ≥ 2.5 % Repr. 2 ;H361f CLP Annex VI (ATP 0) C ≥ 0.5 % STOT RE 2 ;H373 CLP Annex VI (ATP 0) Specific concentration limits DSD lead(II)sulfate C ≥ 2,5 % Repr. Cat. 3; R62 Annex VI C ≥ 1 % Xn; R20/22 Annex VI C ≥ 0,5 % R33 Annex VI The informa on in this safety data sheet is based on data and samples provided to BIG. The sheet was wri en to the best of our ability and according to the state of knowledge at that me. The safety data sheet only cons tutes a guideline for the safe handling, use, consump on, storage, transport and disposal of the substances/prepara ons/mixtures men oned under point 1. New safety data sheets are wri en from me to me. Only the most recent versions may be used. Old versions must be destroyed. Unless indicated otherwise word for word on the safety data sheet, the informa on does not apply to substances/prepara ons/mixtures in purer form, mixed with other substances or in processes. The safety data sheet offers no quality specifica on for the substances/prepara ons/mixtures in ques on. Compliance with the instruc ons in this safety data sheet does not release the user from the obliga on to take all measures dictated by common sense, regula ons and recommenda ons or which are necessary and/or useful based on the real applicable circumstances. BIG does not guarantee the accuracy or exhaus veness of the informa on provided and cannot be held liable for any changes by third par es. This safety data sheet is only to be used within the European Union, Switzerland, Iceland, Norway and Liechtenstein. Any use outside of this area is at your own risk. Use of this safety data sheet is subject to the licence and liability limi ng condi ons as stated in your BIG licence agreement or when this is failing the general condi ons of BIG. All intellectual property rights to this sheet are the property of BIG and its distribu on and reproduc on are limited. Consult the men oned agreement/condi ons for details. Reason for revision: 1.2;8.1;8.2;15.1 Publication date: 2013-05-07 Date of revision: 2013-12-10 Revision number: 0001 Product number: 28902 17 / 17 Annex to theAnnex extended to the SafetySafety Data Data Sheet Sheet (eSDS) >99. Slimes and Sludges, zinc sulfate electrolytic (273-742-8) Sulphuric acid This annex contains information on risk management measures as specified in appendix 3 of the registration dossier for isolated on-site and transported intermediates 1. Brief description of technological process applied in manufacture of the intermediate EC 273-742-8 During the Zinc electrolysis, insoluble oxy-sulphates, (i.e. Lead- & calcium-sulphate and Manganese di- oxide) can be formed at the Lead-anode surface ; part of it falls down in the cells another part sticks to the Lead-anode surface and is separated during the anode-cleaning steps The Pb-Mn cellmud is regularly collected from the bottom of the cells and from the anode-cleaning devices. It is settled, washed and filtered. Transfer of the Pb-Mn cellmud occurs in big-bags or containers or covered bulk load trucks, according to applicable regulation The ‘Pb Mn cellmud’ is a lumpy wet filtercake with an average Lead-content of 20-30% w/w and is typically used in production units of Lead metal (EC 231-100-4) or Lead compounds and recovery of precious metals Waste of the process: - None 2. Brief description of technological processes applied in use of the intermediate EC 273-742-8 The ‘Pb Mn cellmud’ is unloaded from transport trucks, ADR-big-bags or containers, …and transferred to storage silo’s through especially designed transfer units, The ‘Pb Mn cellmud’ is optionally blended with other Lead-containing primary or secondary materials The mixture is continuously fed to smelting furnaces (i.e. ISA, Blast furnace, ISF ...) or similar for further smelting extraction of lead and lead compounds, and precious metals Waste treatment: - None - During pyrometallurgical treatment: slag. The slag is dumped if not re-used in road filling. 3. Means of rigorous containment and minimisation technologies applied by the registrant during the manufacturing and /or use process Description of the technical means to rigorously contain the substance Process enclosures and closed circuits where relevant and possible Containment of liquid volumes in sumps to collect/prevent accidental spillage, acid solutions are treated adequately Potential dryers are operated under strong aspiration (negative pressure towards atmospheric pressure) All processes are performed in a confined area The process is managed and controlled from a separate control-room. Identification of residual emissions to workplace & environment Residual exposures at the workplace and the environment are assessed from regular measurements of dust/metals and represent usually a global exposure to several steps in a process. Dust control: dust and metals in dust needs to be measured in the workplace air (static or individual) according to national regulations. o Workplaces: dust, metal concentrations? Annex – page 1 Product number: 28902 Annex to theAnnex extended to the SafetySafety Data Data Sheet Sheet (eSDS) >99. Slimes and Sludges, zinc sulfate electrolytic (273-742-8) Sulphuric acid o Workers: biomonitoring – blood for Pb, twice a year if appropriate or according to regulation o Environment air: stack point source measurement (dust, metal concentrations) o Environment water: typically measured prior to discharge, if emissions to surface waters are relevant Some non-process waters can be generated containing Mn/Pb (e.g. from cleaning) Description of the procedural and control technologies to minimise emission and resulting exposure The Pb Mn cellmud residue is kept moist, so dust formation/emission is by definition limited In the use phase, where it is dried, air emissions are controlled by use of air emission abatement devices e.g. filters, wet scrubbers. This may create a general negative pressure at the system openings (loading, sampling, production exit). regular sampling, cleaning, maintenance On-site waste water treatment techniques are applied to prevent releases to water (if applicable) e.g.: chemical precipitation, sedimentation and filtration. Local exhaust ventilation systems Special care for the general establishment and maintenance of a clean working environment by e.g.: o Cleaning of process equipment and workshop o Contained storage of leach residue in covered areas All residues formed during the leaching process (and gas-cleaning system at use site), are recovered and either recycled in the system or handled further according to waste legislation Wearing of gloves and protective clothing is compulsory With normal handling of the moist residue, no respiratory personal protection (breathing apparatus) is necessary. Eyes: safety glasses are recommended or compulsory Specification of management means and training that particularly contribute to the functioning of the technical means described above integrated management system is implemented on the workplace e.g. ISO 9000, ISO ICS13100 series, ISO 1400X series, EMAS, or alike and, as usually applicable, by being IPPC-compliant (cf. NFM-BREF) housekeeping and hygiene procedures in place training provided for internal and external cleaning teams or technicians Follow up HS by medical unit: biomonitoring if required (e.g.. Pb, ...) 4. Means of rigorous containment and minimisation technologies recommended to the user of the intermediate Means of containment and minimisation technologies are same as above Blending, and optionally pelletizing, and furnaces are operated under strong aspiration (negative pressure towards atmospheric pressure) The zinc leach residue is unloaded from [pneumatic] transport trucks, train, ADR-big-bags or containers, …and transferred to storage zones or silo’s through especially designed transfer units Material composition, handling, storage procedures and general guidance on safe use are communicated to the personnel or downstream (external) user by means of Safety Data Sheet Annex – page 2 Product number: 28902 Annex to theAnnex extended to the SafetySafety Data Data Sheet Sheet (eSDS) >99. Slimes and Sludges, zinc sulfate electrolytic (273-742-8) Sulphuric acid 5. Special procedures applied before cleaning and maintenance Procedures are in place to ensure safe cleaning and maintenance operations o Stopping (part of) the process o Cooling down and proper ventilation of equipment o Switch off power supply & lock out procedure o Special PPE mandatory for cleaning personnel or maintenance technicians o Planning and training for internal and external personnel general guidance on safe use is communicated to the personnel or downstream (external) user by means of Safety Data Sheet 6. Describe activity and type of PPE in case of accidents, incidents, maintenance and cleaning activities Accident release measures: Workers: Immediately contact emergency personnel. Keep unnecessary personnel away. Use suitable protective equipment. Environment: Avoid dispersal of spilled material and runoff and contact with soil, waterways, drains and sewers. Cleaning: If emergency personnel are unavailable, vacuum or carefully scoop up spilled material and place in an appropriate container for disposal by incineration. Avoid creating dusty conditions and prevent wind dispersal. Fire: Use an extinguishing agent suitable for the surrounding fire. No specific hazard. Fire water contaminated with this material must be contained and prevented from being discharged to any waterway, sewer or drain. Thermal decomposition products are sulfur oxides (SO2, SO3 etc.) and some metallic oxides. Fire-fighters should wear appropriate protective equipment and self-contained breathing apparatus (SCBA) with a full face-piece operated in positive pressure mode. Periodic maintenance: (Furnace and associated equipment if applicable, Off-gas treatment system, Repair operations, Observational tasks and control activities), the following measures are taken: General protective and hygiene measures: Eating, drinking and smoking should be prohibited in areas where this material is handled, stored and processed. Workers should wash hands and face before eating, drinking and smoking. Separate storing of protective / work clothing is necessary. Avoid contact of spilled material and runoff with soil and surface waterways. Use process enclosures, local exhaust ventilation or other engineering controls to keep airborne levels below recommended exposure limits. If user operations generate dust, fumes or mist, use ventilation to keep exposure to airborne contaminants below the exposure limit. Respiratory protection: Use a properly fitted, particulate filter respirator complying with an approved standard if a risk assessment indicates this is necessary. Respirator selection must be based on known or anticipated exposure levels, the hazards of the product and the safe working limits of the selected respirator. Hand protection: Chemical-resistant, impervious gloves complying with an approved standard should be worn at all times when handling chemical products if a risk assessment indicates this is necessary. Personal protective equipment for the body should be selected based on the task being performed and the risks involved and should be approved by a specialist before handling this product. Eye protection : Safety eyewear complying with an approved standard should be used when a risk assessment indicates this is necessary to avoid exposure to liquid splashes, mists, gases or dusts. Body protection: Usual chemical work clothing. Cleaning activity : (Process equipment, workshop): same applies Annex – page 3 Product number: 28902 Annex to theAnnex extended to the SafetySafety Data Data Sheet Sheet (eSDS) >99. Slimes and Sludges, zinc sulfate electrolytic (273-742-8) Sulphuric acid 7. Waste information The intermediate is a product for the production of zinc as a metal. If the normal processing route cannot be adhered to, returning it to the producer is recommended. Disposal should be in accordance with the official regulations (hazardous waste) PPE equipment is collected and disposed of Packaging? Annex – page 4 Product number: 28902 Annex to theAnnex extended to the SafetySafety Data Data Sheet Sheet (eSDS) >99. Slimes and Sludges, zinc sulfate electrolytic (273-742-8) Sulphuric acid Slimes and Sludges, zinc Calcine from roasting process or sulfate electrolytic (273- direct leaching of 742-8) process scheme concentrates Lifecycle of slimes and sludges is illustrated by the colored forms Addition of - limestone/gypsum - sludge thickener - sulphuric acid Leaching and purification steps closed system Spent acid solution Purification Spent acid ZnSO4 solution Pumping of cell mud & solution residues from cells and from cathode cleaning device settler Zinc electrolysis tanks filter storage Optional Pb and Pb transportation to DU- Lead plant compounds site production Annex – page 5 Product number: 28902